Process for producing cement expanding agents

ABSTRACT

Cement expanding agent is produced by burning a raw mixture containing CaO, Al2O3, SO3 and F, wherein the weight ratio of CaO/Al2O3 is 0.5 to 20, 0.2 to 20 percent by weight of an inorganic fluoride and 30 to 80 percent by weight of CaSO4 are contained, in a directly heating electric resistance furnace at the electrode AC voltage of 20 to 400 V and the electrode current density of 0.8 to 8.0 Amp./cm2 and cooling the fused body under a particular condition.

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United States Patent 11 1 1111 3,801,345

Nakagawa 1 Apr. 2, 1974 [54] PROCESS FOR PRODUCING CEMENT 3,251,701 5/1966 Klein; 106/104 3,155,526 11/1964 Klein .1 106/103 EXPANDING AGENTS Koji Nakagawa, Asahi, Japan Denki Kagaku Kogyo Kabushiki Kaisha, Tokyo, Japan Filed: Mar. 30, 1971 Appl. No.: 129,420

Inventor:

Assignee:

US. Cl. 106/314, 106/89 Int. Cl C041) 13/22 Field of Search 106/86, 103, 104, 314

References Cited UNITED STATES PATENTS Primary Examiner-James E. Poer Attorney, Agent, or FirmSughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT Cement expandin a ent is produced by burning a raw mixture containi CaO A160 SO and F, wherein the weight ratio of CaO/A1 O is 0.5 to 20, 0.2 to 20 percent by weight of an inorganic fluoride and 30 to 80 percent by weight of CaSO are contained, in a directly heating electric resistance furnace at the electrode AC voltage of 20 to 400 V and the electrode current density of 0.8 to 8.0 Amp/cm and cooling the fused body under a particular condition.

10 Claims, 6 Drawing Figures PATENIEBAPR 2mm 11801; 345

SHEEI 1 F 4 E FDA B C a Addition percentage L of CuF2(%) C4A3(%)IOO 9'0 8 Yb so 4o 30 2 0 lb 0 IO so I00 02mm) PATENTEBAPR 2:914

saw u or 4 wm&

PROCESS FOR PRODUCING CEMENT EXPANDING AGENTS The present invention relates to a process for producing cement expanding agents, which is characterized in that a raw mixture containing CaO, A1 SO, and F as the chemical components is heated and fused in a directly heating electric resistance furnace and the fused body is cooled under a particular condition.

Heretofore, the cement expanding agent consisting essentially of CaO, M 0 and S0 has been produced in industry in a rotary kiln but in a short period of time after the starting of the operation, the growth of a ring at the burning zone in the kiln is intensive and the continuous operation cannot be carried out.

An object of the present invention is to solve such a defect.

For the purpose, the first means is to define the chemical composition ratio of the raw mixture. Namely, the raw mixture is constituted with the weight ratio of CaO to A1 0 of 0.5 to 20, 0.2 to 20 percent by weight of an inorganic fluoride and 30 to 80 percent by weight of CaSO,. The raw mixture is fused in a directly heating electric resistance furnace.

Furthermore, the present invention is characterized in that the cement expanding agents having the mineral compositions of different constitutions and different crystals can be obtained by cooling the fused body in a variety of manners and this point is a noticeable difference from the conventional process.

When the weight ratio of CaO to A1 0 in the raw mixture is beyond the range from 0.5 to 20, the properties of the quality is considerably deteriorated. Namely, in the case of less than 0.5, unreacted alumina (A1 0 increases, while in the case of more than 20, free calcium oxide (abridged as F-CaO) increases and the stability becomes poor. The definition of CaSO, to 30 to 80 percent by weight based on the total amount is based on the following reason. Since the raw mixture is fused in the directly heating electric resistance furnace, the formation of 80 due to the decomposition increases. Namely, in the case of less than 30 percent, the melting point rises and the generation of S0, is intensive, while in the case of more than 80 percent, the quality of the cement expanding agent lowers.

The addition of the inorganic fluoride provides an absolutely necessary effect in the second means (burning process) as mentioned hereinafter. The effect does not appear in less than 0.2 percent, while when exceeding 20 percent, the quality as the cement expanding agent lowers considerably.

The term inorganic fluorides" used herein means metal compounds containing fluorine or may be the metal compounds, wherein fluorine exists as a coordinate in a complex group, for example, CaF, (fluorite), Na AlF, (cryolite) andthe like, which can be decomposed or sublimated at a temperature of higher than 800 C. The substances, which generate gas at such a temperature, are not preferable. it has been confirmed that K SiF AlF MgF BaF CrF FeF ZnF and the like show substantially the same function.

In the practice of the first means, that is the compounding of the raw mixture, white bauxite and red bauxite are most preferable as the alumina and in addition use may be made of the calcined products of raw materials containing a large amount of alumina, such as alunite, kaolinite, aluminous shale, diaspore and the like and metallic aluminum and aluminum nitride are more preferable alone or in admixture. The metallic aluminums include processing scrap of metallic aluminum and aluminum containing ash, which is byproduced in aluminum smelting and also aluminum nitride is generally contained in aluminum containing ash and is advantageous, because the cost of the raw mixture is remarkably reduced. The metallic aluminum generates the reaction heat due to the oxidation in the course of the subsequent heat treatment and reduces the amount of electric power consumed. Moreover, aluminum nitride improves the fluidity of the fused body and has an excellent function in view of the stable and continuous furnace operation.

However, the compounding ratio of metallic aluminum or aluminum nitride in the raw mixture is preferred to be 0.2 to 20 percent by weight, because the amount of less than 0.2 percent, cannot attain the above described function, while in the amount of more than 20 percent, the unreacted aluminum nitride remains in the product and therefore when the expanding agent is compounded in a cement, a hydrolysis occurs in the course of hydration and ammonia gas (NH is generated and such an amount is not preferable.

As the calcium oxide material, use may be made of any substances containing a large amount of CaO. As gypsum material use may be made of any of natural materials and chemical by-products, if such materials contain a large amount of CaSO,. It is preferable for the stabilization in the following fusing step that the amount of the volatile substances contained in these raw materials, which volatilize at a temperature of lower than C, are small as far as possible.

According to the present invention, the grain size of each raw material is defined in order that the raw mixture having the above described composition ratio can enhance the reaction ratio of alumina and stabilize the quality and enable the continuous operation for a long period of time. It has been found that it is important to balance the average grain sizes of alumina raw material and calcium oxide raw material and the pore volume of the particle assembly.

For example, an explanation will be made with respect to the alumina raw material. When alumina raw material having an extremely large average grain size is used, even if the raw mixture could be burnt, a large amount of unreacted A1 0 remains in the fused body. When the average grain size of the alumina raw material is extremely small, the reaction is rapidly completed but the viscosity of the fused body increases rapidly, the fluidity decreases, the escape of S0 is intensive and the tapping of the fused body from the reaction system becomes very difficult. Accordingly, in the present invention, the average grain size and the pore volume of the alumina raw material are adjusted to be less than 5 mm and 0.05 to 0.5 cm"/g respectively and the grain size of the calcium oxide raw material is adjusted to be 1 to 10 times of the average grain size of the alumina raw material. When the average grain size of the calcium oxide raw material based on the average grain size of the alumina raw material is less than 1, the viscosity of the fused body increases and the tapping is difficult, while when said average grain size value is more than 10, the reaction rate lowers and the heating must be effected for a long time and these sizes are not preferable.

The pore volume" used herein is shown by the volume of the total fine pores within the range of 75A. to 75,000 A. per unit weight of the powder sample and is measured by the mercury porosimeter.

The average grain size is defined by the maximum value of the grain size distribution.

The second means comprises fusing the above described raw mixture by means of the directly heating electric resistance furnace.

The term electric furnace used herein is the furnace in which the raw material is directly heated by using the fused raw mixture as an electric resistor and generally a carbon electrode is used and the furnace has the same system as the furnace for producing calcium carbide or ferroalloy.

The other melting furnaces, for example, a low frequency induction furnace or a high frequency induction furnace may be used but these furnaces need a high cost for electric power and are not advantageous economically.

The temperature of the fused body varies depending upon the chemical composition of the raw mixture but the inventor has studied in detail the mechanism of the fusion reaction of the ternary system of CaO-Al O -CaSO and as the result it has been found that the reaction rate of alumina is improved, the viscosity increases rapidly and the fluidity lowers.

The fused body near the electrode is over heated locally and the escape of S is intensive, so that it is necessary to improve the fluidity of the fused body.

The inventor has succeeded in the improvement of the fluidity by adding 0.2 to percent by weight of an inorganic fluoride to the raw mixture and the escape of SO has been completely prevented. Thus the reaction rate of alumina can be considerably improved. Since the fluidity is improved, the tapping of the fused body from the furnace has become very easy and an important effect has been developed in the course of cooling, which is the third means. The amount of the inorganic fluoride added is adjusted so as to keep the temperature of the fused body within the range of l,450 to l,l00C, whereby the temperature of the fused body can be maintained stably and constantly, even if the variation of the electrode voltage and current occurs.

The term electrode voltage" used herein means the voltage at the top of the electrode and AC voltage of 20 to 400 V is most preferable. The voltage of less than 20 V is not preferable in view of the heat efficiency, while the voltage of more than 400V generates arc intensively and the temperature becomes unusually high and the escape of SO occurs and these voltages are not preferable.

' By the process as described above in detail, the previous defects can be removed and the continuous operation for a long period of time can be effected stably.

When the fused body in the furnace becomes higher than l,450C, the escape of SO begins. In general, the desulfuric acid decomposition reaction of anhydrous gypsum occurs at a temperature within the range of l,380 to l ,3 00C but the inventor has found that when gypsum coexists in the raw mixture, CaSO in gypsum forms an eutectic composition together with the free CaO and the fluoride and is stabilized and therefore the temperature for starting the decomposition rises to about 1,450C even in the fused state under a reducing atmosphere. However, when the load voltage and the electrode current density are not proper, the temperature of the fused body is often unusually raised and the escape of occurs intensively and the chemical composition of the fused body changes and the fluidity is lost.

The inventor has studied in order to solve this problem and it has been found that the electrode current density is most preferred to be 0.2 to 8 Amp/cm? In less than 0.2 Amp./cm the production efficiency per unit hour lowers and the efficiency of the electric furnace lowers, while in more than 8 Amp./cm'-, the operation is unstable, the blowing up phenomenon of the fused body is noticeable and so called flicker" phenomenon occurs.

Then, an explanation will be made with respect to the cooling process, which is the third means. As mentioned above, the composition of the fused body can be freely varied by the variation of the cooling process.

The first process is as follows:

The fused body is flown out and taken on an iron ladle, of which the space between double walls is filled with silica, natural sand, zeolite and the other refractory insulating materials and an upper cover is put on the ladle and the fused body is left to stand. By such a treatment, the cement expanding agent consisting mainly of the mineral composition of C, A -CaO-CaSO is obtained.

The second process is as follows:

The fused body is flowed out into an iron ladle provided with no insulating material or a metal mold ingot and cooled naturally. In this case the cement expanding agent consisting mainly of the mineral composition of C A -C A -C8O-CaSO is obtained,

The above described two cooling processes are referred to as gradual cooling" and if the raw mixture is within the range of ABCD shown in FIG. 1, which is the range of the chemical composition of the present invention, these cooling processes are applicable. The range shown by EJKH is preferable in view of the quality. In the range of JFGK, F-CaO is little and therefore the product which is hardly weathered, is obtained. In this case, C A -CaSO is main and F-CaO is little and particularly on the line of X-Y, the cement expanding agent containing no CaO can be obtained. In this range, the product which cannot only expand cement but also improve the initial strength of cement, is obtained and accordingly this range is distinguished from the range of EJKI-I in view of the quality. In the range of EFGH, the addition of the fluoride is sufficient in an amount of 0.2 to 5 percent by weight. C,,A-, and C A mean l2CaO'7Al O and 3CaO- 3Al O -CaSO respectively.

The inventor has confirmed that the ratio of C A, to C A of the mineral composition of the fused body can be optionally varied by controlling the cooling rate of the fused body and the amount of the inorganic fluoride added.

Namely, a phase equilibrium is established as shown in the following equation.

7(C A 15C 2 3(C A 7CS Q In the actual measurement by the inventor, when Q in the above equation is assumed to be 38 Kcal and the cooling rate of the fused body is low, the phase equilib-' rium transfers to the right side.

The present invention has been accomplished based on the discovery of such a fact and even if the fused body is treated by the same cooling process, the com- 5 position ratio of C A to CAS varies depending upon the content of fluorides.

The relation of the cooling rate and the amount of fluorite to the formation ratio of C, A -C,A S is shown by the graph in FIG. 2. The chemical composition of the raw mixture is adjusted to the mole ratio of CaO:Al O :CaSO being 4:113 and (D), l(A), -3(B) and (C) percent by weight of natural fluorite are added thereto respectively. The case when the fluorite is not added, is shown by the curve D and the composition of the product is not significantly changed by the variation of the cooling rate but when the fluorite is added, for example, when 1 percent of fluorite is added, even if the cooling rate is the same as in the case of no addition of fluorite, the product wherein the ratio of C A decreases and adversely the ratio of C A increases as shown by the curve A, is produced. Furthermore, the smaller the cooling rate, the more intensive the tendency is and the larger the amount of fluorite added (curve B 3 percent, curve C= 5 percent), the more noticeable said tendency is. It has been confirmed that this tendency is substantially the same as in the natural fluorite with respect to the test of the other inorganic fluorides.

The composition ratio of C A to C, A means the ratio of C A to C A, in the alumina containing mineral excluding CaO, CaSO and a trace of C,AF, C 8 and vitreous substances and the quantitative analysis of both the components was effected by means'of X-ray diffraction. C AF means 4CaO-Al O 'Fe O and C 8 means 2CaO-SiO The quantitative analysis was referred to N. Fukuda, J. Ceram. Assoc. Japan, p. 187-191, 69(6), 1961, and was determined from X-ray diffraction intensity ratio based on C,A and C, A which are synthesized from the pure chemicals, by adding percent by weight of l(Cl as the internal standard substance.

The thus obtained cooled body is milled and added to a cement to form an expansive cement, which has a unique property. Namely, the minerals of C,A S and C, A have been heretofore known in the type of coexistence of CaSO or CaO and CaSO and have been used practically but when they are mixed with cement, water and sand, C,,A-, series agent is good in the expandability in the original hydration but is too earlier in practice in the setting time. On the contrary, the setting time of C A S series agent is not different from that of usual Portland cement. The cement expanding agent according to the present invention possesses the merits of both the agents and has improved properties. When the composition ratio of C A becomes predominant, F-CaO is little or if the raw mixture is compounded in the stoichiometric amount within the range as shown in JFGK in FIG. 1, the cement expanding agent consisting mainly of C, A -CaSO, and containing no F-CaO can be obtained. The common characteristics of these agents consist in that they are hardly weathered, and have a high stability, which are different from the conventional agents. 9 percent by weight of various cement expanding agents having different contents of C A and C, A were compounded with usual Portland cement and the mixture was determined with respect to the free expansion coefficient of mortar according to H8 R 5201 and the result is shown in FIG. 3.

As seen from this result, the maximum effect to the expansion coefficient is obtained at the composition ratio of C A to CAS of 2:8 8:2, so that the corresponding cooling rate of the fused body is preferred to be within the range of 2 to 20C/min.

However, such a correct measurement of the cooling rate is difficult and therefore in the practice the cooling is effected by the above described cooling processes 1 and 2 and the fused body is taken out on the ladle and the temperature is adjusted by keeping the temperature from the outside, if necessary or by cooling by air. In short, the cooling is essentially necessary until C A, is formed and after the formation, the gradual cooling is not always necessary and the treatment is effected so as to meet the practical operation.

The third cooling process involves discharging and blowing out the fused body into a compressed air of a pressure of l to 20 Kg/cm to effect a quenching. The resulting cooled body can be obtained freely from lump to particle by varying the air pressure and the shape of air flow (for example, the size and shape of nozzle). The cooled body obtained in this manner consists mainly of CA5 and does not contain C A The chemical composition within the range of EFGH in FIG. 1 provides the product consisting mainly of C A -CaO-CaSO. r C A -CaSO but as the grain size of the cooled bommmaller, the amorphous portion increases and the characteristic diffraction ray of F-CaO remains according to X-ray diffraction and the diffraction pattern of the other minerals are not substantially 'shown. This tendency is particularly distinct in the case of the grain size of less than 5 mm and the cement expanding agent, of which the hydration reaction is very slow, is formed. Accordingly, said agent can be utilized as a non-shrinkable cement in the practice and when said expanding agent is applied to the plaster, the shrinking cracks can be prevented. The product having a grain size of more than 5 mm can be practically used as the excellent cement expanding agent. This agent is somewhat slower in the hydration rate than the conventional expanding agents and shows the expandability for a long period of time. If an explanation will be made with respect to an embodiment having the chemical composition of mole ratio of CaOzAl O :CaSO b eing 4:1 :3, said agen'K showsthe exp'afismas shownbyfhe curve 2 in FIG. 4. The curve 2 shows the case when a mortar sample defined in 115 R 5201 (7 percent by weight of cement expanding agent is compounded to usual Portland cement) is cured in water and even when the sample is left to stand in air (RH to percent) after one week of the water curing, the shrinkage does not occur as shown by the curve 2' (the sample after cured for one week in water is the standard). The curve 1 shows the expansion state in the case when the expanding agent obtained by burning the raw mixture having the same chemical composition as described above is used and the sample was cured in water for the total period of time and the curve 1 shows the expansion state when said sample is left to stand in air after one week of the water curing. The curve 3 shows the expansion state when usual Portland cement is cured in water for the total period of time. The curve 3 will be explained hereinafter.

As seen from the comparative examples, even if the cement expanding agent according to the present invention contains the same amount of F-CaO as the conventional agent, it shows considerably unique properties and this is an important merit of the present invention.

The gas pressure in the blowing away cooling process has relation to the tapped amount of the fused body and cannot be determined in general but in the case of less than I Kg/cm even if said amount is smaller, the

ica] reaction, and 1.5 percent by weight of cryolite were compounded to prepare a raw mixture.

The chemical compositions of the raw materials are shown in the following Table I. In Table I, the numeral pressure is not sufficient to blow away the fused body, 5 means percent by weight.

Table 1 lg. loss Al O CaO S SiO F0 0;, Othcrs Total Quick lime 0.5 95.7 0.2 0.4 L9 0.8 99.5 Bauxite 0.3 86.2 0.3 3.9 5.5 3.4 99.6 Gypsum 1.7 0.3 39.4 57.8 0.3 0.1 0.3 99.6

' body and the like. However, when the fused body is contacted with water for a long time, it is hydrated. Accordingly, it is necessary to separate rapidly water from the cooled body after the cooling. The cooled body in this process shows the expandability as shown by the curve 3 in FIG. 4 and particularly when it is applied to the plastering mortar, the cracking, which is observed in the conventional products, can be prevented and in the other applications, the ideal non-shrinkable cement, which does not show the volume variation, can be obtained.

For a better understanding of the invention, reference is taken to the accompanying drawings, wherein:

FIG. 1 is a graph showing the chemical composition range of the present invention;

FIG. 2 is a graph showing the relation of the cooling rate of the fused body to the resulting mineral composition;

FIG. 3 is a graph showing the relation of the resulting mineral composition to the expansion coefficient;

FIG. 4 is a graph showing the relation of the age to the expansion coefficient, which shows the quality of the expansive cement;

FIG. 5 is X-ray diffraction patterns of the cooled body obtained by the present invention; and

FIG. 6 is a graph showing the relation of the electrode current density of S0 escape ratio.

The following examples are given for the purpose of illustration of this invention and are not intended as limitations thereof.

EXAMPLE 1 Quick lime, bauxite and gypsum having chemical compositions as shown in the following Table l were used as raw materials. 31.9 percent by weight of the quick lime, which passed wholly through a 2 mm mesh sieve and had an average grain size of 0.5 mm, 11.0 percent by weight of the bauxite having an average grain size of 0.13 mm and a pore volume of 0.141 cm lg, 90 percent of which passed through a 0.25 mm mesh seive, 57.0 percent by weight of the gypsum, which was a by-produced anhydrous gypsum in a chem- The above described raw mixture was fused under the following condition by means of a directly heating electric resistance furnace provided with three graphite electrodes and having a maximum load power of 2,000 KVA.

Electrode voltage -250 V Electrode current density l--5A/cm Equivalent resistivity 3-90 Temperature of the fused body 1,250 to l,420C

The resulting fused body was tapped from the furnace and cooled according to the following four processes.

l. The fused body was poured into a crucible-shaped and double-walled iron ladle having an inner capacity of about 0.3 m, which had been filled with natural sand between the two walls, and the ladle was covered and left to stand.

The X-ray diffraction pattern of the resulting cooled product was composed of C, A,, CaO and CaSO as shown in FIG. 5A.

2. The fused body was poured into a box-shaped cast iron metal pattern having an inner capacity of 0.7 m so that the thickness of the fused body was 20 cm and then left to stand.

The cooled product had a composition ratio of C12A1IC4A3 4:6.

3. Compressed air was blown to a flow of the fused body from the back side of the flow through a flat nozzle having a major axis of 45 mm and arranged under the outlet of the furnace under a gauge pressure of 3 to 10 Kg/cm and the fused body was scattered in a cooling iron rotary drum to obtain a granular cooled product. The granules were seived by means of a 5 mm mesh sieve. The X-ray diffraction pattern of the granules passed through the sieve and that of granules not passed through the sieve are shown in FIGS. 5B and 5C, respectively.

4. The fused body was poured between two rotary drums rotating in the opposite direction and arranged under the outlet of the furnace, which drums were similar to a Bessemer twin roll type cooling and coagulationg roll and cooled with water in the interior, and at the same time water was sprayed on the fused body, and then the fused body was passed between the two drums together with the water to obtain a flaky cooled product. The flaky cooled product was separated from the water.

The X-ray diffraction pattern of the resulting flaky cooled product is shown in FIG. 5D.

Chemical analysis showed that all the cement expanding agents obtained by the above described four cooling processes and having the X-ray diffraction patterns shown in FIGS. A, 5B, 5C and 5D had the same pare four kinds of raw mixtures. composition as shown in the following Table 2. In Each raw mixture was put in a platinum dish and Table 2, the numeral means percent by weight. fused at 1,400C in an electric resistance furnace pro- Table 2 Insoluble SiO: A1103 Fe,O CaO MgO SO TiO Total EXAMPLE 2 vided with a carborundum heating element. Then, the Raw materials having the same compositions as load electric power of the furnace was gradually deshown in Table 1 were used. However, as the bauxit creased or stopped to control variously the cooling rate one having previously been pulverized by aball mill so within the range of 2 to 50C/min. The amounts of j; as to adjust the average grain size to be 5.5 mm and I5 C A and C A -,S of the resulting cooled products were having a pore volume of 0.01 m/g measured by a merdetermined by means of a X-ray diffraction method. cury porosimeter was used. The raw materials and Relations between the coohng rate with the composii cryolite were compounded in the same recipe as detion ratio of C A to C A S are shown in FIG. 2. The I scribed in Example 1 and fused under the same condicement expanding agents having predetermined comtion as described in Example I. Chemical composition position ratios of C, A to C A S were pulverized to a i of the resulting cooled product is shown in the follow- Blaine specific surface of about 1,700 cm /g and 7 peri ing Table 3. In Table 3, the numeral means percent by cent by weight of each pulverized expanding agent was weight. compounded with ordinarily used Portland cement so Table 3 i Insoluble sio M203 F5 0. CaO MgO so Tio Total EXAMPLE 3 that the total amount of the resulting expansive cement was 100 percent by weight. The expansion coefficient of the cement was measured by the use of a mortar briquet by means of a dial gauge according to the method described in HS R 520]. The expansion coefficient of 5 the briquet after 2 week age is shown in FIG. 3.

Raw materials having the same compositions as shown in Table l and aluminum containing ash having a composition shown in the following Table 4 (the numeral in Table 4 means percent by weight) were compounded in the following recipe. 3

EXAMPLE 5 The same raw mixture as described in Example 1 was by tested by means of a Girod electric furnace capable of inclining and rotating and having a maximum load Quiclr lime 3L5 power of 450 KVA. The electric furnace was provided Aluminum containing ash 4.9 Gypmm 55] w1th one cylindrical carbon electrode having a diameter of 257 mm.

10 Kg of natural fluorite and a small amount of char- The resulting raw mixture was fused under the same coal were firstly placed under the electrode andarc was condition as described in Example 1. The fused body generated to prepare a fused body at a temperature of had a temperature of 1,350C and had a very good flul,l90C, and then a raw mixture which had previously idity. been prepared was gradually added thereto. It was con- Chemical composition of the resulting cooled prodfirmed from the analysis of the shape of pulsating curuct is shown in the following Table 5. In Table 5, the rent by an oscilloscope that a directly heating electric I numeral means percent by weight. resistance furnace was formed. As the addition of the Table 4 A1 0 F N. 510 Pep, Al Total Table 5 Insoluble A1 0 SO CaO SiO- F620;. MgO TiO: Total Nitrogen content in the cooled product was analysed raw mixture proceeded, a pool formed by the fused by a Kjieldahl method, but nitrogen was not detected. body was larger and the temperature of the fused body reached l,370C. Then to percent of the fused body forming the pool was tapped from the furnace, and the raw mixture was further charged to the fur- EXAMPLE 4 nace. This procedure was repeated and the furnace was To the same raw materials as used in Example 1 were kept under a stable condition. In this case, the electric added 0, 1, 3 and 5 percent by weight of fluorite to precondition was as follows:

The primary voltage) V, 2,200 Volt The primary current I, 25 Amp.

The secondary voltage V 55 Volt and The secondary current 1 was calculated to be 1,000

Amp. without considering the power-factor.

The average load power was calculated to be approximately 55 KW, and the electrode current density CD was calculated to be 1.97 Amp/cm from the following formula 1 CD l /rrr 1. In the above formula I, r (cm) represents the radiusof the electrode.

The resistivity p of the fused body in the furnace was calculated to be 1.86 Q-cm from the following formula The above described seven raw mixtures were fused in the directly heating electric resistance furnace used in Example 5 under the same condition as described in Example 5.

2. l5 Temperatures of the fused bodies were measured by p Rrrr lh V rrr /l h 2. means of an optical pyrometer. The temperature in ex- In the above formula 2, R represents the resistance periment No. I was l,5l0C, that in experiment No. V value in the furnace, and h (cm) represents the diswas l,570C and that in experiment No. VI was 1,400- tance between the lower end of the electrode and the C. In experiment Nos. I, V and VI, though the raw mixbottom of the furnace. The most stable operation was ture contained a large amount of fluorite, the fluidity able to be generally effected in the case that the disof the fused body was considerably poor. The temperatance h was l5 cm. As the result of experiments at varitures of the fused bodies in experiment Nos. II, III, IV ous distances, it was found that an electrode current and VII were within the range of l,l80 to 1,450C. density ranging from 0.2 to 7.0 Amp/cm was most ad- Chemical compositions of the fused bodies are shown vantageous for the operation. When the density was in the following Table 7. In Table 7, the numeral means I less than 0.2 Amp/cm, the furnace efficiency is conpercent by weight.

Table 7 Experiment No. Insoluble Al O 50;, C SiO: Fe O F, Others Total 1 5.8 12.2 3.1 67.0 1.4 2.2 4.4 3.3 99.4 11 0.2 2.1 50.7 43.1 0.4 0.5 0.8 1.2 99.0 111 24.9 7.7 20.0 31.3 2.7 1.6 3.4 1.3 992 IV 0.5 0.7 46.1 49.8 0.2 0.5 1.3 1.1 98.9 v 0.1 4.1 7.8 80.6 2.2 0.9 3.4 0.8 99.9 v1 239 19.9 3.2 40.2 3.2 3.0 3.3 2.2 98.9 V1! 2.8 10.1 45.4 37.4 0.8 0.9 0.7 98.1

siderably low, while the density was about 8.0 In the experiment Nos. I, V and VI, a large amount Amp/cm, a large amount of sulfuric acid anhydride of sulfuric acid anhydride was escaped, and particularly was escaped. The result is shown in FIG. 6. in the experiment Nos. III and VI, a large amount of un- A test was made with respect to the voltage at the top reacted A1 0 was remained, and consequently stable of the electrode ranging from 20 to 400 V. When the operation was not able to be effected for a long period voltage was higher than 400 V, are was formed and a of time.

large amount of sulfuric acid anhydride was escaped In the experiment No. II, fusion was able to be efand consequently stable operation was impossible, feeted, but a major part of the fused body is gypsum while when the voltage was lower than 20 V, the furand such a composition is not suitable to be used as a nace efficiency was low. The term furnace efficiency cement expanding agent. herein described is Show" y the amount of P In the experiment Nos. IV and VII, fusion itself was P L KWD of consumed electric p when able to be effected stably, but the tapping was difficult. continuous operations were effected in both of Exam- F rth r, in the cement expanding agent containing ple l and this Example 5, the furnace efficiency w 3 more than 20 percent by weight of fluorite as shown in to 55. experiment No. I, the expansion coefficient was con- EXAMPLE 6 siderably low. Raw mixtures having a chemical composition outside the range of the present invention were prepared from EXAMPLE 7 raw materials having the same composition as shown in Table l and fluorite in the compounding recipe as b s 9 the cement g i shown in the following Table 6. The fluorite was comy t e gaz i m gf g t at pounded in an amount based on the weight ofa mixture each 9 8 y having an 1 i pattern .of the raw materials only. In Table 6, the numeral m H 5C or 5D i Pu venzed to a means percent by weight Blame spec1fic surface of 2,300 cm /g. 9 percent by weight of the pulverized cooled product was added to Table 6 ordinarily used Portland cement so that the total Expcrimem Quick Bauxite Gypsum amount was percent to prepare an expansive ce- Fluorite ment.

No lime The expansion coefficient of the resulting expansive l 559 23 cement was measured by the use of a mortar briquet of 4X4X1 6 cm according to J 18 R 5201. The expansive cement was mixed with sand in a ratio of cement: and

crete was prepared from the expansive cement in the compounding recipe as shown in the following Table 9.

1:2 and further with water in a water cement ratio of 60 percent, and then the resulting mixture was introduced into a frame having the above dimension and taken out from the frame after cured for 1 day in moist air to obtain the briquet. The expansion coefficient was 15 ficient is shown in the following Table 8. in Table 8, the 20 numeral means percent.

The expansion coefficient of the concrete was measured by the use of rectangular prism briquets of l0Xl0X40 cm having steel ratios of 0, 0.4 and 1.2 percent. The concrete was introduced into a frame having the above dimension, wherein a PC steel rod was arranged in the center portion of the frame along the longitudinal direction of the frame and both ends of the steel rod were fused to flat iron plates of the frame, and taken out from the frame after 24 hours to obtain the briquet. Two points a and b were marked on the briquet, and the briquet was cured in water at 20C for 1 Table 8 Age (day) Sample l 2 4 7 14 21 28 (A) 0.413 0.810 1.463 1.430 1.480 1.491 1.491 (B) 0.052 0.082 0.163 0.328 0.442 0.598 0.061 c) 0.023 0.033 0.048 0.095 0.101 0.112 0.127 (D) 0.017 0.020 0.033 0.047 0.095 0.108 0.114

EXAMPLE 8 week in a room of RH 80 percent for 4 weeks and then In order to clarify the characteristic feature of the present invention, a conventional cement expanding agent obtained by sintering the same raw mixture as de- 35 in water for 1 week. The ratio of the length between the points a and b of the cured briquet to that of the original briquet was measured, which was expansion coefficient. The result of the expansion coefficient measurement is shown in the following Table 10. in Table 10, the numeral means percent, and the sign means shrinkage.

Table 10 Steel in water In a room In water ratio (71) 2 days 7 days 2| days 35 days 36 days 42 days Kiln 0 0.013 0.097 0.070 0.055 0.083 0.083 process 0.4 0.009 0.034 0.012 0.014 0.013 0.014 (control) 1.2 0.004 0.017 0.000 -0.01 8 0.008 0.008 Present 0 0.015 0.075 0.070 0.060 0.074 0.075 invention 04 0.007 0.056 0.042 0.033 0.050 0.050 (expanding 0.005 0.033 0.018 0.008 0.025 0.028

agent B) narily used Portland cement so that the total amount was 100 percent to prepare an expansive cement. Con- The compression strength and the Young's modulus of the concrete are shown in the following Table 11.

The above described strength tests were effected by the use of a cylindrical briquet of 15 X 30cm, which was prepared in an iron frame and cured as such in the same manner as described above.

EXAMPLE 9 Raw materials having the same composition as shown Table 14 1 day 2 days 4 days 7 days l4 days 21 days Present 0.0l8 0.00l 0.02l 0.030 0.048 -0.05l invention (0035) (0.048) (0.093) (0.104) (0.l27) (0131) HS rapid hardening 0.007 0.025 -0.045 0.062 0.095 0. I09 Portland cement (0.001) (0.007) (0.000) (0.002) (0.004) (0.006)

Dreifach 0.0 l 2 0.024 0.047 -().060 -0.097 0.] l5 Z 475 (0.004) (0.008) (0.003) (0.006) [0.012) (0.()l l) in Table l were used. To a mixture of 14.4 percent by EXAMPLE 10 weight of quick lime, 17.0 percent by weight of bauxite and 68.6 percent by weight of gypsum was added 3 percent by weight, based on the weight of the mixture, of

cryolite to obtain a raw mixture. The resulting raw mixture was fused in the same electric furnace as described in Example I. The temperature of the fused body was 1,290C. The fused body was tapped from the furnace into the same double-walled iron ladle as described in the process 1 of Example 1 and cooled gradually.

Chemical composition of the resulting cooled product is shown in the following Table 12. In Table 12, the

The conventional cement expanding agent used in Example 8, which had substantially the same chemical composition as that of the cement expanding agent according to the present invention and was obtained by sintering in a rotary kiln, and the cement expanding agent according to the present invention were compared with respect to the weathering property.

Each expanding agent, which was previously pulverized to a Blaine specific surface of 1,700 cm /g, was left numeral means percent by weight. to stand in air, and the percentage of weight increased Table 12 lnsoluhlc Al- O; CaO SO;X SiO Fe o Others F-CaO The above described cooled product was added with 0.5 percent by weight of CaCl and pulverized to a Blaine specific surface of 6,000 cm /g. 7.0 percent by weight of the resulting mixture was added to rapid hardening Portland cement (corresponding to ASTM, C150 TYP Ill) so that the total amount was 100 percent to prepare an expansive cement. As to the strength of the expansive cement, a mortar briquet was prepared according to .118 R 5201 and cured 1 day in moist air, and the strength of the briquet was measured to obtain a result as shown in the following Table 13.

As a control, the strength of Dreifach Z 475 (trademark, made by Dycker Hoff Co., Germany) was measured in the same manner. The result is also shown in Table l3.

Table 13 Strength (Kg/cm) Time of setting was measured to obtain a result as shown in the following Table 15.

Table 15 Percentage of weight increased Compression Bending lnitiulsel Finuls'ct hrs. min. Present invention 240 50 3 l5 JlS rapid hardening l 30 30 Portland cement Dreifuch 50 Y. 475

hrs. min.

EXAMPLE 11 the expansion coefficient Raw materials having the same compositions as shown in Table 1 were used. To a mixture of 55 percent by weight of quick lime, 6 percent by weight of bauxite and 39 percent by weight of gypsum was added 8% by weight, based on the weight of the mixture, of cryolite to prepare a raw mixture. The raw mixture was fused in the same directly heating electric resistance furnace Curing in water scribed in Example 8. That is, the above described concrete was introduced into a frame having the above dimension, left to stand for 3 hours in a room, heated up to 65C with steam at a rate of 15C/hr. together with the frame, kept at this temperature for 3 hours, cooled to 20C at a rate of 15C/hr. and then taken out from the frame to obtain the briquet. Two points a and b were marked on the briquet, and the briquet was cured in water at 20C for 1 week and then left to stand for 10 4 weeks in a room. The expansion coefficient was shown by the ratio of the length between the points a and b of the cured briquet to that of the original briquet measured by a dial gauge. The obtained result is shown in the following Table 18. in Table 18, the numeral means percent.

As a control, concretes were prepared by the use of the cement expanding agents A and B in Example 7, and the expansion coefficients of these concretes were measured in the same manner as described above. The

result is also shown in Table 18.

Table 18 Left to stand in a mom 4.. My.-." u

1 day 2 days 4 days 7 days 2 weeks 3 weeks 4 weeks Example 11 0.127 0.127 0.134 0.136 0.129 0.123 0.120

Example 7 as used in Example 5. The temperature of the fused body was 1,3 80C and the fused body had a good fluidity. The fused body was quenched by blowing with compressed air under the same condition as described in the process 3 of Example 1. Chemical composition of the quenched product is shown in the following Table 16. In Table 16, the numeral means percent by weight.

As seen from Table 18, when the expansive cement in this Example 11, which contains the quenched cement expanding agent, is used in the production of secondary cement products or shaped articles, such as lining of iron pipe and Hume concrete pipe, which require curing with steam, cement products or shaped articles having an improved chemical prestress can be obtained, and further cracks of lining can be prevented,

Table 16 Insoluble A1,0,, C a0 SO SiO, Fe,0, Others Total The quenched product was pulverized to a Blaine specific surface of about 1,700 em /g. 13 parts by weight of the pulverized quenched product was added to 87 parts by weight of ordinarily used Portland cement to prepare an expansive cement. Concrete was prepared from the expansive cement in the compounding recipe as shown in the following Table 17.

and strength of the shaped articles can be increased.

What is claimed is: l. A process for producing cement expanding agents having a mineral composition predominantly of 12 CaO'7AI O -CaO-CaSO which comprises fusing at temperature of from 1,l00 to 1,450C. a raw material mixture having a weight ratio of ammo, of 0.5 to 20 The expansion coefficicnt of the thus obtained conand containing 30 to percent by weight of (12180,

crete was measured by the use of a briquet of 10 l0 40 cm, which held a PC steel rod of 11 mm in a steel ratio of 1.0 percent in the same manner as deand 0.2 to 20 percent by weight of an inorganic fluoride in a directly heating resistance furnace at an electrode AC voltage of 20 to 400 V and an electrode current density of 0.8 to 8.0 AmpJcm to form a fused body,

and cooling the fused body by an insulated cooling.

2. A process for producing cement expanding agents having a mineral composition predominantly of 12 CaO7Al O CaSO which comprises fusing at a temper 5 ature of from 1,] to l,450C. a raw material mixture having a weight ratio of CaO/Al o of 0.8 to 2.0 and a containing 50 to 70 percent by weight of CaSO and 0.2 to percent by weight of an inorganic fluoride in a directly heating resistance furnace at an electrode AC voltage of 20 to 400 V and an electrode current density of 0.8 to 8.0 Amp./cm to form a fused body and cooling the fused body by an insulated cooling.

3. A process for producing cement expanding agents of an amorphous product which comprises fusing at a temperature of from l,l00 to l,450C a raw material mixture having a weight ratio of CaO/Al O of 0.5 to 20 and containing 30 to 80 percent by weight of CaSO and 0.2 to 20 percent by weight of an inorganic fluoride in a directly heating resistance furnace at an electrode AC voltage of 20 to 400 V and an electrode current density of 0.8 to 8.0 Amp/cm to form a fused body and cooling the fused body with water.

4. The process as claimed in claim 1, wherein said in- I sulated cooling is by allowing said fused body to cool in an area insulated from ambient conditions.

5. The process as claimed in claim 2, wherein said insulated cooling is by allowing said fused body to cool in an area insulated from ambient conditions.

6. The process as claimed in claim 1, wherein the amount of CaSO Al O and C210 in said raw material mixture is within the area of EJKH in FIG. 1 and the amount of the inorganic fluoride in said raw material mixture is 0.2 to 5 percent by weight.

7. The process as claimed in claim 2, wherein the amount of CaSO Al O and CaO in said raw material mixture is on the line X-Y of FIG. 1.

8. The process as claimed in claim 1, wherein the alumina raw material has an average grain size of less than 5 mm and a pore volume of 0.05 to 0.5 cm' /g and the calcium oxide raw material has an average grain size of 1 to 10 times the average grain size of the alumina.

9. The process as claimed in claim 2, wherein the alumina raw material has an average grain size of less than 5 mm and a pore volume of 0.05 to 0.5 em /g and the calcium oxide raw material has an average grain size of l to 10 times the average grain size of alumina.

10. The process as claimed in claim 3, wherein the alumina raw material has an average grain size of less than 5 mm and a pore volume of 0.05 to 0.5 cm /g and the calcium oxide raw material has an average grain size of l to 10 times the average grain size of alumina. =8 t 1F 

2. A process for producing cement expanding agents having a mineral composition predominantly of 12 CaO.7Al2O3-CaSO4, which comprises fusing at a temperature of from 1,100* to 1,450*C. a raw material mixture having a weight ratio of CaO/Al2O3 of 0.8 to 2.0 and containing 50 to 70 percent by weight of CaSO4 and 0.2 to 5 percent by weight of an inorganic fluoride in a directly heating resistance furnace at an electrode AC voltage of 20 to 400 V and an electrode current density of 0.8 to 8.0 Amp./cm2 to form a fused body and cooling the fused body by an insulated cooling.
 3. A process for producing cement expanding agents of an amorphous product which comprises fusing at a temperature of from 1,100* to 1,450*C a raw material mixture having a weight ratio of CaO/Al2O3 of 0.5 to 20 and containing 30 to 80 percent by weight of CaSO4 and 0.2 to 20 percent by weight of an inorganic fluoride in a directly heating resistance furnace at an electrode AC voltage of 20 to 400 V and an electrode current density of 0.8 to 8.0 Amp./cm2 to form a fused body and cooling the fused body with water.
 4. The process as claimed in claim 1, wherein said insulated cooling is by allowing said fused body to cool in an area insulated from ambient conditions.
 5. The process as claimed in claim 2, wherein said insulated cooling is by allowing said fused body to cool in an area insulated from ambient conditions.
 6. The process as claimed in claim 1, wherein the amount of CaSO4, Al2O3 and CaO in said raw material mixture is within the area of EJKH in FIG. 1 and the amount of the inorganic fluoride in said raw material mixture is 0.2 to 5 percent by weight.
 7. The process as claimed in claim 2, wherein the amount of CaSO4, Al2O3 and CaO in said raw material mixture is on the line X-Y of FIG.
 1. 8. The process as claimed in claim 1, wherein the alumina raw material has an average grain size of less than 5 mm and a pore volume of 0.05 to 0.5 cm3/g and the calcium oxide raw material has an average grain size of 1 to 10 times the average grain size of the alumina.
 9. The process as claimed in claim 2, wherein the alumina raw material has an average grain size of less than 5 mm and a pore volume of 0.05 to 0.5 cm3/g and the calcium oxide raw material has an average grain size of 1 to 10 times the average grain size of alumina.
 10. The process as claimed in claim 3, wherein the alumina raw material has an average grain size of less than 5 mm and a pore volume of 0.05 to 0.5 cm3/g and the calcium oxide raw material has an average grain size of 1 to 10 times the average grain size of alumina. 